단축키

단축키

Decarbonylation of Os5(CO)14(PPh3) by 2 equiv of Me3NO/CH3CN at room temperature followed by reaction with C60 in refluxing chlorobenzene produces Os5C(CO)11(PPh3)(μ3,η2:η2:η2-C60) (1) in 44% yield. Thermal treatment of 1 at 80 °C under 1 atm of carbon monoxide affords Os5C(CO)12(PPh3)(μ,η2:η2-C60) (2) in good yield (72%). Upon thermolysis of 2 at 132 °C, 2 is cleanly reconverted to 1 (73%) by loss of a carbonyl ligand. Reaction of 1 with benzyl isocyanide at room temperature gives the addition product Os5C(CO)11(CNCH2C6H5)(PPh3)(μ3,η2:η2:η2-C60) (3) in 85% yield. Thermolysis of 3 at 100 °C forms the isomeric Os5C(CO)11(CNCH2C6H5)(PPh3)(μ,η2:η2-C60) (4) in 64% yield. Treatment of 4 with 1 equiv of Me3NO/CH3CN at room temperature followed by heating at 132 °C in chlorobenzene gives Os5C(CO)10(CNCH2C6H5)(PPh3)(μ3,η2:η2:η2-C60) (5) in 71% yield. Compound 5 can be alternatively prepared from the reaction of 1 with excess Ph3PNCH2Ph at room temperature in 59% yield. Heating a chlorobenzene solution of 5 at 55 °C under 3 atm of carbon monoxide produces 4 as the only major product (16%). Treatment of Ru5C(CO)11(PPh3)(μ3,η2:η2:η2-C60) (1‘) with benzyl isocyanide at room temperature forms Ru5C(CO)11(CNCH2C6H5)(PPh3)(μ3,η2:η2:η2-C60) (3‘) in 90% yield. Reaction of 1‘ with benzyl isocyanide at a slightly elevated temperature of 40 °C affords Ru5C(CO)10(CNCH2C6H5)(PPh3)(μ3,η2:η2:η2-C60) (5‘) in an almost quantitative yield of 96%. Compounds 1−5, 3‘, and 5‘, isolated as crystalline solids, have been characterized by microanalytical and spectroscopic methods. Molecular structures of 1−4 and 5‘ have been elucidated by X-ray crystallographic studies.

A mono- to di- and triphosphane transformation occurs on treatment of [Ir4(CO)9(PPh3)3] (1) with C60 to successively afford 2 and 3. The noninnocent, multifunctional C60 ligand plays a crucial role in transforming three PPh3 ligands into...

Highly crystalline and monodisperse MnO and Mn3O4 nanoparticles are prepared by thermal decomposition of [Mn(acac)2] in oleylamine under an inert atmosphere in the presence and absence of a small amount of water, respectively (see pictur...

The reaction of Ir4(CO)8(PMe3)4 with excess C60 in refluxing 1,2-dichlorobenzene, followed by treatment by CNR (R = CH2C6H5) at 70 °C, affords a fullerene−metal sandwich complex Ir4(CO)3(μ4-CH)(PMe3)2(μ-PMe2)(CNR)(μ-η2,η2-C60)(μ4-η1,η1...

A three-dimensional networked osmium nanomaterial (N-Os) was prepared by a thermal decomposition of Os3(CO)12 within mesopores of MCM-48. The novel N-Os species shows high catalytic activity and excellent reusability in the oxidat...

Highly crystalline and monodisperse In2O3 nanoparticles have been prepared by thermal decomposition of In(acac)3 in oleylamine under inert atmosphere. The particle size of In2O3 can be easily manipulated by changing the experimental cond...

Thermal decomposition of W(CO)6 in oleylamine in the presence of mild oxidant Me3NO·2H2O produces tungsten oxide nanorods with diameters ranging from 3 to 6 nm. The size of nanorods can be easily varied by the employed surfactant ratio...

[60]Fullerene can bind a variety of metal clusters via η2-C60, μ-η2:η2-C60, and μ3-η2:η2:η2-C60 π-type bonding modes. Multiple C60 additions to a single cluster core have also been demonstrated. Modification of the coordination sphere of clu...

The reaction of Os3(CO)9(μ3-η2:η2:η2-C60) (1) with PhCH2NPPh3 in chlorobenzene affords the benzyl isocyanide substituted product Os3(CO)8(CNR)(μ3-η2:η2:η2-C60) (2a, R = CH2Ph) in 76% yield. Photolysis of 1 in the presence of an excess of...

22. [60]Fullerene as a Versatile Four-Electron Donor Ligand

H. Song, K. Lee, M.-G. Choi, and J. T. Park

Organometallics, 2002, 21, 1756

A new 1,2-σ-type C60 compound, Os3(CO)7(CNR)(μ3-CNR)(PPh3)(μ3-η1:η1:η2-C60) (2; R = CH2Ph), is formed from Os3(CO)8(CNR)(μ3-CNR)(μ3-η1:η2:η1-C60) (1) upon substitution of CO with PPh3 on a triosmium cluster framework. Compounds 1 and 2 a...

21. The First Fullerene-Metal Sandwich Complex: An Unusually strong Electronic Communication between Two C60 Cages

Reaction of Rh6(CO)9(dppm)2(μ3-η2,η2,η2-C60) (1) with C60 in refluxing chlorobenzene followed by treatment with CNR (R = CH2C6H5) at room temperature affords the first fullerene−metal sandwich complex Rh6(CO)5(dppm)2(CNR)(μ3-η2,η2,η2-C60)...

20. Reversible Interconversion between m,h2,h2- and m3,h2,h2,h2-C60 on a Carbido Pentaosmium Cluster Framework

K. Lee, Z.-H Choi, Y.-J. Cho, H. Song, and J. T. Park

Organometallics, 2001, 20, 5564

Decarbonylation of Os5(CO)14(PPh3) by 2 equiv of Me3NO/CH3CN at room temperature followed by reaction with C60 in refluxing chlorobenzene produces Os5C(CO)11(PPh3)(μ3,η2:η2:η2-C60) (1) in 44% yield. Thermal treatment of 1 at 80 °C under ...

The reaction of C60 with Re3(μ-H)3(CO)11(NCMe) in refluxing chlorobenzene produces Re3(μ-H)3(CO)9(μ3-η2,η2,η2-C60) (1) in 50% yield. Initial decarbonylation of 1 with Me3NO/MeCN followed by reaction with PPh3 in boiling chlorobenzene aff...

18. First Example of the μ3-η1,η2,η1-C60 Bonding Mode: Ligand-Induced Conversion of π to σ C60–Metal Complexes

H. Song, K. Lee, C. H. Lee, J. T. Park, H. Y. Chang, and M. G. Choi

Angew. Chem. Int. Ed., 2001, 40, 1500

A boat-shaped 1,4-cyclohexadiene-like ring is present in the C60 molecule with a novel σ-typeμ3-η1,η2,η1 bonding mode in the clusters 2 a and 2 b. The change in coordination mode was induced by insertion of an RNC ligand into an Os−Os bo...

15. Reversible Interconversion between m3-h2,h2,h2- to m-h2,h2-C60 on a Carbido Pentaosmium Cluster Framework

K. Lee, C. H. Lee, H. Song, J. T. Park, H. Y. Chang, and M.-G. Choi

Angew. Chem. Int. Ed., 2000, 39, 1801

Carbonyl addition or elimination reactions on an Os5C cluster framework result in a novel interconversion between two C60 bonding modes: μ3-η2,η2,η2-C60 for 1 and μ-η2,η2-C60 for 2. The latter bonding mode had been elusive until now, and...

The title complex, Os3(CO)6(PMe3)3(μ3-η2,η2,η2-C60) (3), has been prepared by decarbonylation of Os3(CO)9(μ3-η2,η2,η2-C60) with three equivalents of Me3NO in the presence of excess PMe3 ligand. The solid-state structures of Os3(CO)7(PMe3)2(μ...

Reaction of MMe3 (M=Al, Ga) with one equivalent of NH2NPh2 affords a dimeric complex [Me2M-μ-N(H)NPh2]2 [M=Al (1), M=Ga (2)] as a mixture of trans and cis isomers. Purification of 1 and 2 by recrystallization gives only trans isomers 1a and ...

12. Synthesis and Characterization of (CH3C(CH2PPh2)3)RhH(h2-C60)

H. Song, K. Lee, J. T. Park, and I.-H. Suh

J. Organomet. Chem., 1999, 584, 361

The title complex, (triphos)RhH(η2-C60) (2) (triphos=CH3C(CH2PPh2)3), was prepared by the reaction (80°C, toluene) of C60 with a trihydride rhodium complex (triphos)RhH3(1) in high yield (86%) as green crystals and characterized by spectrosc...

Two μ3-η2,η2,η2-C60 complexes, Os3(CO)8(PPh3)(μ3-η2,η2,η2-C60) (8) and Os3(CO)7(PMe3)2(μ3-η2,η2,η2-C60) (9), have been prepared by decarbonylation of Os3(CO)9(μ3-η2,η2,η2-C60) (6) with Me3NO/MeCN in the presence of phosphine ligands. The...

The substitution of carbonyl ligands in the edge-shared bioctahedral cluster [PPN]2[Ru10C2(CO)24] by two types of 4e donor π-bonding ligands, viz., a diene (norbornadiene) and an alkyne (diphenylacetylene), has been investigated under va...

9. Reversible transformation between Methylene and Methylidyne-Hydride on the Ru10C2 Framework

K. Lee, S. R. Wilson, and J. R. Shapley

Organometallics, 1998, 17, 4113

Oxidative substitution of [Ru10C2(CO)22(NBD)]2- with ferrocenium/diazomethane forms a methylene derivative, Ru10C2(CO)22(NBD)(CH2), in which the methylene ligand symmetrically bridges two adjacent apical ruthenium centers in the e...

8. Substitution of [Ru10C2(CO)24]2- with Allene. Reversible Formation of [Ru10C2(CO)22(C3H4)2- and [Ru10C2(CO)20(C3H4)2]2

K. Lee and J. R. Shapley

Organometallics, 1998, 17, 4030

Substitution of carbonyl ligands in [Ru10C2(CO)24]2- (1) by allene proceeds cleanly in diglyme at 90 °C (1 atm) to afford the monosubstituted derivative [Ru10C2(CO)22(μ-η2:η2-C3H4)]2- (2). Treatment of either 1 or 2 with allene at...

Interaction of C60 with Ru5C(CO)15 or PtRu5C(CO)14(COD) in hot chlorobenzene, followed by treatment with solubilizing phosphines, provides compounds with hexahapto coordination of C60 to a Ru3 face of the square pyramidal Ru5C or octahed...

2. Coordination of C60 to Penta- and Hexaruthenium Cluster Frames

K. Lee, H.-F. Hsu, and J. R. Shapley

Organometallics, 1997, 16, 3876

In refluxing chlorobenzene C60 reacts with
Ru5C(CO)15 or with Ru6C(CO)17 to form new complexes,
which are isolated following treatment with tertiary
phosphines to give the structurally characterized, facebonded
derivatives Ru5C(CO)11(PPh...

1. Characterization and structures of intermediates in the reactivity of CpWOs3(CO)11(μ3-CTol) towards dihydrogen and water

Initial decarbonylation of CpWos3(Co)11(μ3-CTol) (1: Cp = η5-C5H5, Tol = p-C6H4Mc) with the Me3NO/MeCN followed by reaction with dihydrogen and water produces a dihydrido comlex CpWOs3(CO)10(μ3-CTol)(μ-H)2 (2), a ‘butterfly’ cluster with a 6...